CN101863455B - Plate type plasma reactor for hydrogen production through ammonia decomposition - Google Patents

Plate type plasma reactor for hydrogen production through ammonia decomposition Download PDF

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CN101863455B
CN101863455B CN2010101658956A CN201010165895A CN101863455B CN 101863455 B CN101863455 B CN 101863455B CN 2010101658956 A CN2010101658956 A CN 2010101658956A CN 201010165895 A CN201010165895 A CN 201010165895A CN 101863455 B CN101863455 B CN 101863455B
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reactor
ammonia
discharge
plate
electrode
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CN101863455A (en
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郭洪臣
赵越
王丽
宫为民
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Dalian University of Technology
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Dalian University of Technology
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Abstract

The invention belongs to the technical field of plasma chemistry and hydrogen energy, and relates to a plate type plasma discharge reactor for hydrogen production through ammonia decomposition. The plasma reactor is characterized by being divided into a plat-plate type, a needle-plate type and a pipe-plate type according to different earth electrodes, wherein an insulating blocking medium is arranged between a high-voltage electrode and the earth electrode of the reactor, and open pores are formed on the blocking medium; the high-voltage electrode and the earth metal electrode generate plasmas to discharge through the open pores on the blocking medium to ensure that ammonia gas is decomposed into hydrogen gas and nitrogen gas in a discharge zone; and the open pores of the blocking medium not only are discharge channels, but also are inevitable channels for reactants. The plate type plasma discharge reactor with the blocking medium provided with the open pores has the advantages of reducing the discharge voltage, limiting the discharge zone, improving the energy density of the discharge zone, and further improving the efficiency of decomposing the ammonia gas directly by using non-equilibrium plasmas.

Description

A kind of plate type plasma reactor that is used for preparing hydrogen by ammonia decomposition
Technical field
The invention belongs to plasma chemistry and Hydrogen Technology field, relate to a kind of plate type plasma reactor that can be used for the ammonia decomposing hydrogen-production.
Background technology
The exhaustion day by day of fossil energy such as coal, oil and natural gas, and the harm of directly using these fossil energy emission greenhouse gases and environmental pollutant to cause force people must constantly pursue clean energy.The Application and Development of Hydrogen Energy receives global attention just under this background.This is because can hydrogen almost be converted into electric energy under the normal temperature efficiently through utilizing Proton Exchange Membrane Fuel Cells (PEMFC).What in this conversion process, take place is the cell reaction that hydrogen and oxygen generate water.Utilize the advantage of Hydrogen Energy to comprise with fuel cell: (1) hydrogen and oxygen are not direct burning when operation of fuel cells; But through the electrochemical appliance generating; Therefore its energy conversion efficiency is not limited by carnot's working cycle; Theoretical efficiency can reach 83%, and actual efficiency can reach 50-60%, is 2-3 times of the actual efficiency of ordinary internal combustion engine; (2) discharge water during operation of fuel cells, normal temperature work down can not produce NOx yet.Therefore utilize Hydrogen Energy through fuel cell, not only efficiently but also be zero release.
A lot of open source literatures and patent documentation relate to the hydrogen-oxygen fuel cell technology.As: Renewable and Sustainable Energy Reviews, 13 (2009) 1301-1313; J.Power SourCes, 2,006 155 (2) 340-352; Current Opinion in Solid State and MaterialsScience 6 (2002) 389-299; CN200920001509.2; CN200920038575.7; CN200820033377.7; CN200820078884.2; CN200720188454.1; CN200720013599.8; CN200620049568.3; CN200620068780.4; CN200520133025.5; CN200520047642.3; CN200480033325.4; CN200480037015.9; CN200380100425.X; CN02159650.6; CN01126123.4; CN00816543.2; CN97199582.6; CN86100407.
Yet fuel cell technology wants to realize popularization and application, also is faced with numerous challenges.Comprising hydrogen source problem and hydrogen production process problem.Up to now, the hydrogen source of having reported both at home and abroad mainly is based on the carbon back hydrogen source of fossil oil and biomass.For example, following hydrogen source has been proposed: Sweet natural gas, conventional liq fuel (diesel oil, boat coal, gasoline), alcohols (ethanol, methyl alcohol) and dme.Obtain hydrogen by above-mentioned hydrogen source and can use the steam reforming technology.
A lot of open source literatures and patent documentation relate to the method and the technology of fossil resource hydrogen manufacturing such as Sweet natural gas, alcohols, coal, gasoline, diesel oil.As: Chem.Rev.107 (2007) 3952-3391; Chemical Industry And Engineering Progress 28 (2009) 1169-1174; CN200720104594.6; CN200710048432.X; CN200410053885.8; CN200410081348.4; CN200410031348.4; CN96102205.1; CN89106847.3; CN200810107531.5; CN200610013035.4; CN200610130484.7; CN200610130277.1; CN200510041633.8; CN200310115196.0; CN200810034740.1; CN200710037410.3; CN200710046067.9; CN200510041633.8; CN200510022208.4; CN00816840.7; CN200910039095.7; CN200910303502.0; CN200810184969.3; CN200820181786.1; CN200710202589.3; CN200710036748.7; CN01138906.0.
Also there are open source literature and patent documentation all to relate to biomass hydrogen preparation.As: International Journal of Hydrogen Energy 32 (2007) 3238-3247; Hydrogen Energy, 199823 (7) 551-557; Hydrogen Energy 199823 (8) 641-648; CN200910116565.0; CN200910028748.1; CN200810195544.2; CN200810137399.2; CN200710016668.5; CN200410005733.0; CN200310100892.4.
In such as large chemical complexes such as synthetic ammonia, methyl alcohol, the steam reforming technology is a very sophisticated traditional industry technology, is mainly used in fossil feedstock such as coal, Sweet natural gas are changed into synthetic gas (hydrogen, carbon monoxide or carbonic acid gas).There are many open source literatures and patent to relate to the steam reforming technology specially.As: Applied Catalysis A:General, 2007333 (2) 114-121; CN200910045202.7; CN200810107529.8; CN200810107530.0; CN200710203190.7; CN00121571.X.Steam reforming is a power consumption step.The direct fuel cell method that directly utilizes carbon-based fuel (like methyl alcohol, ethanol) is also arranged.With methyl alcohol is example, directly fuel cell method be exactly with methyl alcohol replace hydrogen in fuel cell with oxygen generation electrochemical reaction.But this method battery efficiency is low, the easy carbon monoxide poisoning of electrode catalyst, and development difficulty is bigger.
But, use the maximum problem of carbon back hydrogen source to be that it not only consumes Nonrenewable resources, and do not touch the greenhouse gas emission problem that consumption fossil fuel tape comes at all.When retail was consumed again with the concentrated hydrogen manufacturing of large-scale steam reforming technology, the carbon dioxide greenhouse gas discharging occurred in production link; When disperseing hydrogen manufacturing (like vehicle-mounted hydrogen production) with miniature steam reforming technology, the carbon dioxide greenhouse gas discharging occurs in user's link.
In recent years, ammonia is regarded as the non-carbon back hydrogen source of ideal by increasing people.With ammonia hydrogen manufacturing following advantage is arranged: the energy density of (1) ammonia high (the maximum specific energy of ammonia splitting gas is 5.59KWh/Kg, the maximum specific energy 3.8KWh/Kg of methanol steam reforming gas); (2) green degree is high (has only H in the ammonia splitting gas 2And N 2, can make not emission greenhouse gas of fuel cell); (3) light (the 1Kg H of fuel load 2Consumption 5.67Kg ammonia.But then will consume 5.17Kg methyl alcohol and 3.0Kg water to methanol steam reforming, the cracking of fuel load ratio ammonia exceeds 44%);
(4) ammonia at room temperature pressure to reach 0.8MPa be that liquefiable and ignition range are narrower, security is better, is suitable for accumulating.Time-honored ammonia synthesizing industry has been set up perfect ammonia conveying method and facility.
In addition, NH 3Still a kind of large Chemicals are cheap and easy to get.The present age, the synthetic ammonia technology was very ripe, and present single series synthetic ammonia installation the biggest in the world has reached 1,300,000 t/a, and throughput is huge, spreads all over all over the world.
Theoretical according to transition state, synthetic ammonia catalyst also can be used as ammonia decomposition catalyzer.Using the most general synthetic ammonia catalyst in the industry is traditional F e 3O 4The base fused iron catalyst had developed ruthenium-based catalyst in recent years again.In fixed-bed reactor, utilizing conventional thermocatalysis method to decompose ammonia (reversed reaction of synthetic ammonia) is the research focus of current ammonia cracking hydrogen production.
A lot of open source literatures relate to the conventional thermocatalysis method with ammonia hydrogen manufacturing.As: Catal.Today, 77 (2002) 65-78.; Chem.Eng.J.93 (2003) 69-80.; Chem.Rev.104 (2004) 4767-4790.; Catal.Letter 72,3-4 (2001) 197-201.; Appl.Catal.A:General, 227 (2002) 231-240.; Appl.Catal.A:General 277 (2004) 1-9.; Int.Eng.Chem.Res., 43 (2004) 74-84.; Energy technology 26,3 (2005) 102-105.; Catalysis Communications 6 (2005) 229-232.; Appl.Catal.A:General 301 (2006) 202-210.; Appl.Catal.A:General 320 (2007) 166-172.Applied Catalysis B:Environmental 80 (2008) 98-105.; Catal.Lett128 (2009) 72-76.
A lot of patent documentations also relate to conventional thermocatalysis method and decompose ammonia hydrogen manufacturing.For example:
Disclosed a kind of integral ammonia decomposition hydrogen producing catalyst and preparation method thereof in the Chinese invention patent (application number 200710047827.8).It is characterized in that: this catalyzer is with pickling process metallic nickel or metallic nickel and rare earth oxide to be carried on the alumina supporter that is strapped in the steel fiber network structure to make.Catalyzer with this patented process preparation need use under the high temperature more than 600 ℃.
Disclosed a kind of load type metal nickel catalyzator that is used for preparing hydrogen by ammonia decomposition in the Chinese invention patent (application number 200610027050.4).It is characterized in that: catalyzer contains rare earth oxide 1%-20%, nickel %-20%, carrier 60%-98%, is a kind of loaded catalyst.Carrier is Al 2O 3, SiO 2, gac or silico-aluminate.Catalyzer with this Patent publish method preparation need use under 500-600 ℃ high temperature.
Disclose ammonia in the Chinese invention patent (application number 200510031519.7) and decomposed high-efficient carrier nanometer catalyst of system zero COx hydrogen and preparation method thereof.It is characterized in that: catalyzer contains 0.5-40% active ingredient, 0-30% auxiliary agent and 50-95% carrier.The preferred transition metal ruthenium of its active ingredient (Ru), iron (Fe), rhodium (Rh) and nickel (Ni); Preferred lanthanum trioxide (the La of auxiliary agent 2O 3), cerium oxide (CeO 2), Neodymium trioxide (Nd 2O 3), carrier is a solid super base, preferred Na/NaOH/ γ-Al 2O 3, K/KOH/ γ-Al 2O 3And Na/KOH/ZrO 2Catalyzer uses in conventional fixed bed, and temperature of reaction is more than 400 ℃.
Disclosed Catalysts and its preparation method in the Chinese invention patent (application number 03143112.7) with ammonia decomposition reaction preparation zero COx hydrogen.It is characterized in that: catalyzer contains 0.5-20% active ingredient, 0-20% auxiliary agent and 70-99% carrier and constitutes.Wherein, the metal nitride that active ingredient is selected from precious metal and has precious metal character, preferred noble ruthenium (Ru), Noble Metal Rhodium (Rh) and molybdenum nitride (MoN); Carrier is a carbon nanotube; Auxiliary agent is selected from basic metal, earth alkali metal and rare earth compound.Carry out in conventional fixed-bed reactor with the hydrogen manufacturing of above-mentioned catalyst decomposes ammonia.Catalyzer with this patented process preparation need use under 470 ℃-550 ℃ high temperature.
Disclose low temperature modification ammonia in the Chinese invention patent (application number 03134691.X) and decomposed the Catalysts and its preparation method for preparing hydrogen.It is characterized in that: catalyzer contains 0.1-30% active ingredient, 0-20% auxiliary agent and 60-99% carrier.Wherein, the metal nitride that active ingredient is selected from transition metal and has precious metal character, preferred noble ruthenium (Ru), Noble Metal Rhodium (Rh), base metal nickel (Ni) and molybdenum nitride (MoN); Carrier is a nanocrystal metal oxide, preferred aluminum oxide (Al 2O 3), Natural manganese dioxide (MgO), zirconium white (ZrO 2) and zinc oxide (ZnO); Auxiliary agent is selected from basic metal, earth alkali metal and rare earth compound.This patent proposes to replace carbon nanotube as support of the catalyst with nanocrystal metal oxide on its patent (application number 03143112.7) basis in early stage, and purpose is to reduce the catalyzer cost.Carry out in conventional fixed-bed reactor with the hydrogen manufacturing of above-mentioned catalyst decomposes ammonia.Catalyzer with this patented process preparation will use under 480 ℃-550 ℃ high temperature.
A kind of Ni-based preparing hydrogen by ammonia decomposition nitrogen mixed gas Preparation of catalysts methods and applications have been disclosed in the Chinese invention patent (application number 02155943.0).It is characterized in that: main catalyst component is nickel (Ni), and carrier is silicon oxide (SiO 2) or aluminum oxide (Al 2O 3), auxiliary agent is one or more in IA, IIA, IIIB, VIII or the REE.Catalyzer uses in conventional fixed bed, and temperature of reaction is 650 ℃.
Disclosed a kind of ruthenium base preparing hydrogen by ammonia decomposition nitrogen mixed gas Catalysts and its preparation method in the Chinese invention patent (application number 02155944.9).It is characterized in that: the Primary Catalysts active ingredient is ruthenium (Ru), and carrier is silicon oxide (SiO 2), aluminum oxide (Al 2O 3), Natural manganese dioxide (MgO), quicklime (CaO), titanium oxide (TiO 2) or gac; Auxiliary agent is one or more in IA, IIA, IIIA, IVA and the REE.Catalyzer uses in conventional fixed bed, and temperature of reaction is more than 500 ℃, and the use temperature more catalyst based than traditional nickel decreases.
Disclosed a kind of high-activity ommonia decomposition catalyst in the Chinese invention patent (application number 98114265.6).It is characterized in that: catalyzer is made up of active ingredient and carrier.Wherein, active ingredient is molybdenum and nickel, and carrier is aluminum oxide (Al 2O 3) or Natural manganese dioxide (MgO).Its characteristic also has: catalyzer will carry out preparatory nitriding treatment before use under whole temperature is 650 ℃-750 ℃ high temperature, make MOX be converted into metal nitride.Carry out under conventional fixed-bed reactor and the high temperature more than 600 ℃ with above-mentioned catalyst decomposes ammonia.
Disclosed the method and apparatus of producing hydrogen with liquefied ammonia among International Patent Application WO 2008002593 A2.It is characterized in that liquefied ammonia is via the catalyzer thermolysis, the hydrogen of generation is compressed storage, and unreacted ammonia reacts through reclaiming the unit again, but the catalyzer thermolysis is carried out under higher temperature.
European patent EP 1003689 B1 have disclosed a kind of alloy catalyst with the ammonia preparing hydrogen by decomposing, and this catalyzer has Zr 1-xTi xM 1M 2Structure, M1 and M2 are selected from Cr respectively, Mn, Fe, Co, Ni, x=0-1, the ammonia decomposition temperature is between 500 ℃-1000 ℃
Disclosed among International Patent Application WO 01/87770 A1 with ammonia produce hydrogen from thermal decomposition process.It is characterized in that: make ammonia get into the reaction zone of reactor drum with oxygen-containing gas, reaction zone is equipped with ammonia decomposition catalyzer.Virgin gas with the catalyzer contact process in be decomposed into hydrogen and nitrogen, the heat absorption of this process; Meanwhile, make a part of hydrogen that generates in the heat release of reaction zone internal combustion, thereby remedy the heat that the ammonia decomposition course is absorbed.Wherein, At least contain a kind of metal in iron (Fe), cobalt (Co), nickel (Ni), cadmium (Cr), manganese (Mn), platinum (Pt), palladium (Pd), rhodium (Rh) and the ruthenium (Ru) in the ammonia decomposition catalyzer; The carrier of catalyzer is carbon and MOX, and the temperature of reaction of ammonia decomposition catalyzer is at least more than 500 ℃.
U.S. Pat P5055282 has disclosed a kind of Ru/Al with alkali metals modified 2O 3Catalyst system and preparation method thereof, the use temperature of catalyzer are lower than 500 ℃.
U.S. Pat P4704267 has disclosed a kind of technology with ammonia hydrogen manufacturing.It is characterized in that use an adiabatic metal hydride cells to purify and generate the hydrogen in the product gas from the ammonia resolving cell, the ammonia resolving cell adopts calandria type fixed bed reactor.
A kind of apparatus and method have been disclosed among U.S. Patent application US 2004/0154223 A1 with ammonia hydrogen manufacturing.It is characterized in that reactor drum is divided into reaction chamber and combustion chamber, can carry out heat exchange between the two.The ammonia decomposition catalyst can be seated in the reaction chamber as fixed bed, also can be applied to the reaction chamber internal surface, forms catalyst film, and the activeconstituents of ammonia decomposition catalyzer is ruthenium Ru) or nickel (Ni).Combustioncatalysts is housed in the combustion chamber, and its activeconstituents is platinum (Pt).Hydrocarbon fuel is burnt under the combustioncatalysts effect, for the ammonia decomposition reaction provides heat.The ammonia decomposition need be carried out under 550 ℃-650 ℃.
Disclosed a kind of ammonia cracker that is used to produce hydrogen in the U.S. Patent application (US 2003/0232224 A1).Its principal character does, the metal catalyst with the alumina globule load is housed in the ammonia cracker, and the loaded metal activeconstituents is selected from nickel (Ni), ruthenium (Ru) and platinum (Pt), and service temperature is between 500-750 ℃.
Although above-mentioned ammonia cracking hydrogen production route seems fine, it become can popularization and application technology still need face following challenge: (1) contemporary ammonia synthesizing industry is a raw material with fossil resources such as coal and Sweet natural gases still, has unsustainable property problem.And, though ammonia carbon containing not itself, also emission greenhouse gas not during with ammonia hydrogen manufacturing, ammonia synthesizing industry itself will discharge great amount of carbon dioxide greenhouse gas.Therefore, be that the ammonia of raw material production is uncleanly in essence with fossil resources such as coal and Sweet natural gases; (2) though the hydrogen manufacturing of conventional thermocatalysis method decomposition ammonia is feasible technically, and the active low reaction temperatures of non-precious metal catalyst is high, noble metal catalyst is scarcity of resources then.Therefore, big with conventional thermocatalysis method decomposition ammonia hydrogen manufacturing limitation on using.
To the problem that conventional thermocatalysis method exists, we propose to decompose ammonia hydrogen manufacturing with combine with the catalyzer plasma-catalytic technology of formation of nonequilibrium plasma in Chinese invention patent (application number 200610200563.0).It is characterized in that ammonia decomposition reaction carries out, and non-precious metal catalyst is loaded on the region of discharge in the reactor drum in a line cartridge type dielectric barrier discharge plasma catalyticreactor.The result shows that the plasma physical efficiency that dielectric barrier discharge produces directly causes a part of ammonia to decompose at low temperatures.In addition, the catalyzer that is installed in region of discharge can also make a part of ammonia decompose through conventional thermocatalysis approach by means of the electric heating that produces in the discharge process.Moreover, be installed between base metal and the nonequilibrium plasma of region of discharge and have the concerted catalysis effect, thereby significantly improve the activity that the non-precious metal catalyst thermocatalysis decomposes ammonia.
Plasma body is by electronics, negative ions, and the non-condensed system that neutral particles such as radical and ground state and excited state molecule and atom are formed is material the 4th attitude.Plasma body can be divided into high-temperature plasma and low-temperature plasma.Low-temperature plasma is a nonequilibrium plasma, and the thermodynamic temperature of its electronics is generally up to tens thousand of degree, and other heavy particle is then near normal temperature.Nonequilibrium plasma can utilize the radiative collision of its high-energy electron to make reactant molecule excite near under the normal temperature, ionization, dissociate, thereby causes radical formula chemical reaction.Nonequilibrium plasma can use common methods such as high pressure pulse discharge, dielectric barrier discharge, radio frequency discharge and microwave discharge to produce.Wherein, dielectric barrier discharge uses because of even being higher than under the atmospheric condition at normal atmosphere, and discharge reactor is simple in structure, does not need vacuum apparatus, thereby practical and convenient.Owing to can make whole reaction system keep lesser temps with nonequilibrium plasma technology initiating chamical reaction; Reduced requirement to equipment; Save energy and realization easily are so the nonequilibrium plasma technology has obtained application at aspects such as environment protection, material modification and preparations in recent years.There are many patent documentations to relate to the nonequilibrium plasma technology in these Application for Field.As,
Europatent (EP 0900591 B1) has disclosed a kind of in order to produce the plasma discharge reactor having of ozone, methyl alcohol or synthetic gas; Plate-plank frame is adopted in this invention; Between bare electrode, add catalyzer during use, or after covering one deck block media on the side pole plate, add catalyzer again.
Disclosed the low temperature plasma hydrogen preparation method that a kind of water is raw material in the Chinese invention patent (application number 200710112312.1).Its principal character is, sends into water vapour in the nonequilibrium plasma generating unit, makes water molecule activation, decomposition with the nonequilibrium plasma that forms in the device, generates hydrogen and oxygen.Described nonequilibrium plasma adopts the dielectric barrier discharge that adds glass plate or glass jacket structure between the plate electrode.
Chinese invention patent (application number 200820241118.3) has disclosed a kind of discharge plasma off gas treatment reactor drum; It is characterized in that; It comprises at least one reactor unit; Reactor unit comprises upper and lower battery lead plate, between last bottom crown, is stacked with catalyst plates, and the surface of catalyst plates is the catalyst activity component layer.In this invention, catalyst plates plays block media, forms dielectric barrier discharge.
Chinese invention patent (application number 02151229.9 application number 02151228.0) has disclosed a kind of atmospheric low-temperature plasma treatment unit that is used for fiber surface modification.It is characterized in that this treater mainly is made up of four parts: a pair of coolable plane discharge electrode, two interelectrode two parallel dielectric impedance plates, two reactant gases conduits, two gas guide boards.In this invention, add two parallel block medias between two plate electrodes, produce stable dielectric barrier discharge.
Chinese invention patent (application number 02116648.X) has disclosed a kind of multiple plasma generating device.It is characterized in that, be high-pressure stage with the medullary ray electrode, and parallel plate or cartridge type electrode twine line-plate or the line-cartridge type discharge that the insulating bag cortex forms as earthing pole and on line electrode.In this invention, the insulating bag cortex serves as medium, forms dielectric barrier discharge.
Chinese invention patent (application number 02151299.X) has disclosed a kind of no medium low-temperature plasma processed food device.It is characterized in that the wire wire that employing tabular metal and Duo Gen are parallel to the tabular metal is as positive and negative electrode.What this invention was adopted is line-board-like bare electrode plasma discharge, does not have medium between the positive and negative electrode.
Chinese invention patent (application number 03137764.5) disclosed a kind of to the air in the air conditioner ventilation pipeline purify, sterilization, disinfectant device.It is characterized in that the square body by stainless steel plate constitutes is equipped with active oxygen generator and anion generator in the square body, be provided with high density active oxygen district between active oxygen generator and the anion generator.The left and right side frame of active oxygen generator is provided with flat positive electrode plate and needle-like negative electrode plate.High frequency, high-voltage power supply are connected to the needle electrode plate respectively and flat battery lead plate formation effluve generation electron beam forms first barrier, the electric shock kill pathogens.In this invention is unobstructed medium corona discharge.
Chinese invention patent (application number 00819715.6) disclosed a kind of can be under normal temperature and normal pressure easily with effectively to like the sterilization equably of sterilization object such as cereal and seed, and can not make the sterilizing unit and the method thereof of sterilization object compromised quality.It is characterized in that the discharge lateral electrode of forming by a plurality of needle electrodes and separate and form by the ground connection lateral electrode that the plate electrode of insulcrete covering surfaces is formed with the discharge lateral electrode.In this invention, the discharge between needle electrode and the plate electrode is carried out under dielectric impedance.
Chinese invention patent (application number 200610104653.X) has disclosed a kind of dielectric barrier discharge low-temperature plasma indoor air purification method that utilizes the dielectric barrier discharge plasma of introducing magnetic field to remove airborne obnoxious flavour.It is characterized in that reaction electrode adopts needle plate electrode, insert a dielectric-slab in the plate electrode side and realize dielectric barrier discharge.
Disclosed a kind of reaction of low temperature plasma device of handling volatile organic waste gas in the Chinese invention patent (application number 200720149297.3).It is characterized in that the high voltage terminal of reactor drum has plank frame, be provided with a plurality of feed nozzles above, handicapping retaining medium sets out gas port on two sides of reactor shell between high-pressure stage nozzle and ground connection pole plate.In this invention, the discharge between high-pressure stage nozzle and the ground connection pole plate is carried out under dielectric impedance.
Disclose a kind of corona discharge in the Chinese invention patent (application number 200510200418.8) and removed nitric oxide production method.It is characterized in that two electrodes of reactor drum are nozzle-plank frames, not handicapping retaining medium between nozzle-plate electrode.
Disclosed a kind of governing direct-current corona discharge smoke reactor drum in the Chinese invention patent (application number 200410054044.9).It is characterized in that reactor drum is rectangular parallelepiped, air inlet/outlet is established at two ends, in establish a plurality of corona discharges unit, board-like high voltage terminal and ground-electrode are established in each unit, establish a plurality of discharge nozzles on the two-plate, not handicapping retaining medium between electrode.
But; Up to now; Only have several pieces of open source literatures to relate to the ammonia Study on Transformation under the discharge such as dielectric impedance, its interest is to remove NOx gas in the atmosphere [like Plasma Process.Polym.2 (2005) 193-200] and ammonia decomposition mechanism [like InternationalJournal of Mass Spectrometry 233 (2004) 19-24.] with ammonia plasmas.Not seeing as yet with hydrogen manufacturing is the nonequilibrium plasma ammonia disaggregate approach of purpose.
In addition, up to now,, only retrieve following two pieces of other people patents and relate to the hydrogen manufacturing of plasma decomposes ammonia except that our early stage the patent of invention:
U.S. Pat P7037484 B1 has disclosed the plasma reactor of a kind of cracking ammonia or other hydrogen-rich gas hydrogen.It is characterized in that; The inside of plasma reactor is divided into two chambeies with the dielectric medium diaphragm; Plasma body is produced by microwave generator, and microwave generator is through launching electromagnetic energy in first chamber of sky alignment, and electromagnetic energy is passed dielectric diaphragm and in second chamber, produced plasma discharge; Make the ammonia or other virgin gas that inject second chamber decompose generation hydrogen, do not have catalyzer to get involved in the reactor drum.This patent only advances an idea, and does not have embodiment.
Disclosed the device of producing hydrogen and nitrogen with liquefied ammonia among International Patent Application WO 2007119262 A2.It is characterized in that reactor drum is made up of three reaction cavities, ammonia carries out conventional thermocatalysis and decomposes in preceding two cavitys, in the 3rd cavity, carries out microwave plasma and decomposes.The hydrogen that generates is supplied with alkaline fuel cell and is used.The working temperature of this device is between 250 ℃-950 ℃.This invents complex structure, and wherein the thermolysis ammonia is carrying out under the high-temperature very much.
In the nonequilibrium plasma technology, the structure of discharge reactor is to influence the high-energy electron energy distribution, and then influences the key factor of nonequilibrium plasma usefulness.With regard to direct decomposition ammonia, the plasma body usefulness of the line cartridge type dielectric barrier discharge reactor drum that we use in the invention in early stage is very low.Board-like discharge reactor is the another kind of reactor types that often adopts in the nonequilibrium plasma technology.Board-like discharge reactor can be divided into plate-board-like, pin-board-like and three kinds of situation of pipe (nozzle)-plate-type reactor.Plate-type reactor is simple in structure, and processing easily is convenient to amplify.But board-like discharge reactor or two interpolars reported have block media, promptly produce nonequilibrium plasma with dielectric barrier discharge; Or the unobstructed medium of two interpolars, promptly produce nonequilibrium plasma with corona discharge.The former current consumption is big, and usefulness is low.The latter discharges violent but is unstable, and often has light beam to vacillate in the region of discharge, and radiation is strong, to electronics serious interference on every side.
Summary of the invention
The invention provides a kind of plate type plasma reactor that is used for preparing hydrogen by ammonia decomposition, improve the usefulness that nonequilibrium plasma directly decomposes ammonia.We find, use the board-like discharge reactor that has block media, and perforate on block media, can reduce sparking voltage, and the restriction electrical discharge zone improves the energy density of region of discharge, and then improves the usefulness that nonequilibrium plasma directly decomposes ammonia.
Technical scheme of the present invention is following:
The block media plate of at least one perforate is set between high voltage terminal and ground-electrode.The distance of itself and two electrodes can be regulated arbitrarily.The dielectric impedance plate is divided into two portions with reactor drum, amplifies for the ease of reactor drum, offers the ammonia feed mouth in earthing pole one side, offers the splitting gas discharge port in high-pressure stage one side; Perforate on the block media plate is a discharge channel, is again the reactant necessary channel.
The high voltage terminal of plate-type reactor and ground-electrode can be taked following three kinds of modes:
(1) high voltage terminal of plate-type reactor and ground-electrode are respectively two metal sheets.Two metal electrode boards are fixed in the housing of reactor drum abreast.Vertical range between two plates is an interpole gap, on the reactor wall of earthing pole one side, offers the ammonia feed mouth; On the reactor wall of high-pressure stage one side, offer the splitting gas discharge port.
(2) high voltage terminal of plate-type reactor is a metal sheet, and earthing pole is a metal wire.To be fixed on abreast in the housing of reactor drum as the metal sheet of vertical fixing earthing pole metal wire on the metal sheet of high-pressure stage and the center of area; The grounded metal endpoints is an interpole gap to the distance of electrode plate with high voltage, on the reactor wall of earthing pole one side, offers the ammonia feed mouth; On the reactor wall of high-pressure stage one side, offer the splitting gas discharge port.
(3) high-pressure stage of plate-type reactor is a metal sheet, and earthing pole is a metal tube.To be fixed on abreast in the housing of reactor drum as the metal sheet of vertical fixing earthing pole metal tube on the metal sheet of high-pressure stage and the center of area.The mouth of pipe of grounded metal pipe is an interpole gap to the distance of electrode plate with high voltage, amplifies for the ease of reactor drum, also can be with the double ammonia feed mouth of doing of grounded metal pipe; On the reactor wall of high-pressure stage one side, offer the splitting gas discharge port.
More than three kinds of situations, the angle of block media plate and two electrodes can be regulated arbitrarily and can obviously do not influenced reaction effect; The metal sheet center of area of the position of opening of block media plate and ground-electrode or earthing pole metal wire (pipe) are relative.
The desirable 0.5-15 millimeter of two interpole gaps of above-mentioned reactor drum, preferred 4-8 millimeter; The external diameter scope of the diameter of earthing pole metal wire or metal tube is the 0.5-20 millimeter, preferred 2-6 millimeter; The bore size 0.5-30 millimeter of block media plate, preferred 2-8 millimeter.Ammonia feed mouth size range is the 0.5-10 millimeter, preferred 2-6 millimeter; Splitting gas discharge port size range is the 0.5-12 millimeter, preferred 2-8 millimeter.
The housing of above-mentioned reactor drum is processed with insulating material such as quartz, hard glass, alumina-ceramic, tetrafluoroethylene or the metal and the nonmetallic composite that meet the high voltage electric insulating Design.The metal sheet of metal electrode board, earthing pole metal wire (pipe) and solid ground electrode and reactor shell etc. are used the place of metallic substance; With any surface finish, physical strength is high, high temperature resistant and the metallic substance that chemical reaction do not take place with the plasma body of ammonia and ammonia degradation production (like hydrogen) is processed preferred various stainless materials.The block media plate with any surface finish, heat-resisting, physical strength is high and the insulating material that chemical reaction do not take place with the plasma body of ammonia and ammonia degradation production (like hydrogen) is processed preferred glass, quartz, hard glass, epoxy resin, mica or alumina-ceramic.The shape and size of reactor shell can confirm that the amplification of reactor drum realizes through the parallelly connected number that increases above-mentioned reactor drum according to actual needs.The external covering insulation material of reactor enclosure.
The performance of reactor drum of the present invention can use following method to measure:
At first, be connected with AC power according to the common requirement of the effluve high voltage terminal with reactor drum, ground-electrode is connected with ground wire.Then, liquid ammonia storage tank is connected with the ammonia feed mouth of reactor drum through reducing valve, mediation valve and under meter, the splitting gas of reactor drum is flowed out by discharge port.Then, open liquid ammonia storage tank, make liquefied ammonia through reducing valve decompression gasification, its flow is controlled with variable valve, is indicated by under meter.After treating that ammonia reaches stability of flow in reactor drum, open high-voltage power supply, progressively improve the voltage of reactor drum, in reactor drum, produce stable discharge.At this moment, can be observed generation streamer plasma discharge between high voltage terminal and the ground-electrode.Make discharge under certain power, begin after about 15 minutes to form, calculate the ammonia transformation efficiency with the normalization method of nitrogen-atoms with nitrogen in the thermal conductivity cell gc on-line analysis reaction product and unconverted ammonia volume.
The invention has the beneficial effects as follows: perforate has fettered the scope of discharge on the block media plate, has improved the electron energy density of nonequilibrium plasma, and has significantly reduced the sparking voltage that is added on the reactor drum, has improved the energy efficiency that ammonia decomposes.Reactor drum with unobstructed medium is compared, and reactor drum discharge of the present invention is more stable, and harmful radiation is few.Stop that with conventional media reactor drum compares (referring to not perforate of block media), reactor drum of the present invention (referring to the block media perforate) discharge current density improves 6-8 doubly.
Description of drawings
Fig. 1 is plate-plate-type reactor structural representation.
Fig. 2 is pin-plate-type reactor structural representation.
Fig. 3 is a pipe-plate-type reactor structural representation.
Among the figure: 1 metal high-voltage discharging electrode; 2 insulated enclosure materials; 3 reactor shell; 4 dielectrics; 5 virgin gass inlet; 6 heat-insulation and heat-preservation materials; 7 wire ground electrodes; 8 grounding wires; The outlet of 9 splitting gases; 10 high voltage power supplies.
Embodiment
Be described in detail specific embodiment of the present invention below in conjunction with technical scheme and accompanying drawing.
Embodiment 1
Anhydrous liquid ammonia is drawn through reducing valve from storage tank, make the ammonia flow velocity reach 40 ml/min through under meter and mediation valve control, (Fig. 1) sends into the plate plasma discharge reactor from inlet mouth 5.The metal sheet discharge electrode 1 of reactor drum and 7 adopts common stainless steel, 50 millimeters of diameters, 3 millimeters of thickness; Insulated enclosure 2 between itself and the reactor shell adopts polytetrafluoroethylmaterial materials; 4 millimeters of two metal electrode interpole gaps, the insulation block media plate of 3 millimeters of center of area perforates of parallel placement between two metal electrodes, dielectric is selected quartz material for use; Thick 1 millimeter, all be 1.5 millimeters with the distance of electrode plate with high voltage and ground connection pole plate.On the reactor wall between earthing pole and the block media plate, offer the ammonia feed mouth, 1.5 millimeters of diameters; On the reactor wall between high-pressure stage and the block media plate, offer the splitting gas discharge port, 1.5 millimeters of diameters.The housing 3 usefulness polytetrafluoroethylmaterial materials of this reactor drum are processed, 70 millimeters of external diameters, 60 millimeters of internal diameters, 50 millimeters of region of discharge diameters.The outer heat-insulation and heat-preservation material of housing adopts asbestos.Ammonia gets into reactor drum by opening for feed 5, through the perforate on the block media, exports 9 outflow reactors via splitting gas again.After ammonia flow is stablized in the question response device; Give high voltage power supply 10 energisings; Then through voltage regulator, frequency regulator and X-former on the high-voltage power supply; Ac high-voltage progressively is loaded on the metal sheet high-voltage discharging electrode 1 of reactor drum, between the metal high-voltage discharging electrode 1 of reactor drum is through aperture on the insulation block media 4 and metal sheet earthing pole 7, produces ebb-flow discharge.Discharge parameter is set at: 60 volts of the initial voltages of X-former, discharge frequency 13 kilohertzs.Then high-voltage power supply power reaches 18 watts, and actual discharge voltage is 4.6 kilovolts, and the temperature-stable of stable reaction post-reactor is at 127 ℃, and the ammonia rates of decomposing and transforming reaches 43%.
Embodiment 2
Repeat embodiment 1, but discharge parameter is set at: 70 volts of the initial voltages of X-former, discharge frequency 13 kilohertzs.Then high-voltage power supply power reaches 21 watts, and actual discharge voltage is 4.9 kilovolts, and the temperature-stable of stable reaction post-reactor is at 139 ℃, and the ammonia rates of decomposing and transforming reaches 47%.
Embodiment 3
Repeat embodiment 1, but discharge parameter is set at: 80 volts of the initial voltages of X-former, discharge frequency 13 kilohertzs.Then high-voltage power supply power reaches 24 watts, and actual discharge voltage is 5.4 kilovolts, and the temperature-stable of stable reaction post-reactor is at 148 ℃, and the ammonia rates of decomposing and transforming reaches 52%.
Embodiment 4
Repeat embodiment 1, but discharge parameter is set at: 100 volts of the initial voltages of X-former, discharge frequency 13 kilohertzs.Then high-voltage power supply power reaches 28 watts, and actual discharge voltage is 6.0 kilovolts, and the temperature-stable of stable reaction post-reactor is at 213 ℃, and the ammonia rates of decomposing and transforming reaches 56%.
Embodiment 5
Repeat embodiment 1, but change the feed ammonia airshed into 100ml/min, discharge parameter is set at: 60 volts of the initial voltages of X-former, discharge frequency 13 kilohertzs.Then high-voltage power supply power reaches 18 watts, and actual discharge voltage is 4.9 kilovolts, and the temperature-stable of stable reaction post-reactor is at 120 ℃, and the ammonia rates of decomposing and transforming reaches 19%.
Embodiment 6
Repeat embodiment 5, but discharge parameter is set at: 70 volts of the initial voltages of X-former, discharge frequency 13 kilohertzs.Then high-voltage power supply power reaches 21 watts, and actual discharge voltage is 5.3 kilovolts, and the temperature-stable of stable reaction post-reactor is at 135 ℃, and the ammonia rates of decomposing and transforming reaches 24%.
Embodiment 7
Repeat embodiment 5, but discharge parameter is set at: 80 volts of the initial voltages of X-former, discharge frequency 13 kilohertzs.Then high-voltage power supply power reaches 24 watts, and actual discharge voltage is 5.9 kilovolts, and the temperature-stable of stable reaction post-reactor is at 142 ℃, and the ammonia rates of decomposing and transforming reaches 27%.
Embodiment 8
Repeat embodiment 5, but discharge parameter is set at: 100 volts of the initial voltages of X-former, discharge frequency 13 kilohertzs.Then high-voltage power supply power reaches 28 watts, and actual discharge voltage is 6.4 kilovolts, and the temperature-stable of stable reaction post-reactor is at 202 ℃, and the ammonia rates of decomposing and transforming reaches 30%.
Embodiment 9
Repeat embodiment 1, but change the interpole gap of high-pressure stage discharge plate and earthing pole discharge plate into 6 millimeters, the distance of dielectric and electrode plate with high voltage and ground connection pole plate all becomes 2.5 millimeters.Discharge parameter is set at: 60 volts of the initial voltages of X-former, discharge frequency 13 kilohertzs.Then high-voltage power supply power reaches 19 watts, and actual discharge voltage is 5.1 kilovolts, and the temperature-stable of stable reaction post-reactor is at 130 ℃, and the ammonia rates of decomposing and transforming reaches 45%.
Embodiment 10
Repeat embodiment 9, but discharge parameter is set at: 80 volts of the initial voltages of X-former, discharge frequency 13 kilohertzs.Then high-voltage power supply power reaches 26 watts, and actual discharge voltage is 6.2 kilovolts, and the temperature-stable of stable reaction post-reactor is at 156 ℃, and the ammonia rates of decomposing and transforming reaches 55%.
Embodiment 11
Repeat embodiment 1, but change the interpole gap of high-pressure stage discharge plate and earthing pole discharge plate into 10 millimeters, the distance of dielectric and electrode plate with high voltage and ground connection pole plate all becomes 4.5 millimeters.Discharge parameter is set at: 100 volts of the initial voltages of X-former, discharge frequency 13 kilohertzs.Then high-voltage power supply power reaches 32 watts, and actual discharge voltage is 7.0 kilovolts, and the temperature-stable of stable reaction post-reactor is at 186 ℃, and the ammonia rates of decomposing and transforming reaches 66%.
Embodiment 12
Repeat embodiment 1, but change the interpole gap of high-pressure stage discharge plate and earthing pole discharge plate into 15 millimeters, the distance of dielectric and electrode plate with high voltage and ground connection pole plate all becomes 7 millimeters.Discharge parameter is set at: 120 volts of the initial voltages of X-former, discharge frequency 13 kilohertzs.Then high-voltage power supply power reaches 43 watts, and actual discharge voltage is 7.8 kilovolts, and the temperature-stable of stable reaction post-reactor is at 201 ℃, and the ammonia rates of decomposing and transforming reaches 71%.
The comparative example 1
Anhydrous liquid ammonia is drawn through reducing valve from storage tank, make the ammonia flow velocity reach 40 ml/min through under meter and mediation valve control, (Fig. 1) sends into the plate plasma discharge reactor from inlet mouth 5.The structure and parameter of reactor drum is identical with embodiment 1, but changes the perforate medium into complete medium, and is placed on the high-pressure stage metal sheet surface.Ammonia gets into reactor drum by opening for feed 5, and the air in the metathesis reactor exports 9 outflow reactors by splitting gas.After ammonia flow is stablized in the question response device; Give high voltage power supply 10 energisings; Then through voltage regulator, frequency regulator and X-former on the high-voltage power supply; Ac high-voltage progressively is loaded on the metal sheet high-voltage discharging electrode 1 of reactor drum, between the metal high-voltage discharging electrode 1 of reactor drum and metal sheet earthing pole 7, produces dielectric barrier discharge (being thread discharge).Discharge parameter is set at: 30 volts of the initial voltages of X-former, discharge frequency 13 kilohertzs.Then high-voltage power supply power reaches 36 watts, and actual discharge voltage is 9.9 kilovolts, and the temperature-stable of stable reaction post-reactor is at 138 ℃, and the ammonia rates of decomposing and transforming reaches 4%.
The comparative example 2
Repeat comparative example 1, but discharge parameter is set at: 40 volts of the initial voltages of X-former, discharge frequency 13 kilohertzs.Then high-voltage power supply power reaches 48 watts, and actual discharge voltage is 10.5 kilovolts, and the temperature-stable of stable reaction post-reactor is at 171 ℃, and the ammonia rates of decomposing and transforming reaches 11%.
The comparative example 3
Repeat comparative example 1, but discharge parameter is set at: 50 volts of the initial voltages of X-former, discharge frequency 13 kilohertzs.Then high-voltage power supply power reaches 57 watts, and actual discharge voltage is 11.3 kilovolts, and the temperature-stable of stable reaction post-reactor is at 233 ℃, and the ammonia rates of decomposing and transforming reaches 17%.
The comparative example 4
Repeat comparative example 1, but discharge parameter is set at: 60 volts of the initial voltages of X-former, discharge frequency 13 kilohertzs.Then high-voltage power supply power reaches 65 watts, and actual discharge voltage is 11.9 kilovolts, and the temperature-stable of stable reaction post-reactor is at 298 ℃, and the ammonia rates of decomposing and transforming reaches 20%.
The comparative example 5
Repeat comparative example 1, but change the complete medium in the reactor drum into two by one, be placed on respectively on electrode plate with high voltage and the grounding electrode plate.Discharge parameter is set at: 30 volts of the initial voltages of X-former, discharge frequency 13 kilohertzs.Then high-voltage power supply power reaches 40 watts, and actual discharge voltage is 10.7 kilovolts, and the temperature-stable of stable reaction post-reactor is at 166 ℃, and the ammonia rates of decomposing and transforming reaches 2%.
The comparative example 6
Repeat comparative example 5, but discharge parameter is set at: 40 volts of the initial voltages of X-former, discharge frequency 13 kilohertzs.Then high-voltage power supply power reaches 52 watts, and actual discharge voltage is 11.4 kilovolts, and the temperature-stable of stable reaction post-reactor is at 234 ℃, and the ammonia rates of decomposing and transforming reaches 6%.
The comparative example 7
Repeat comparative example 5, but discharge parameter is set at: 50 volts of the initial voltages of X-former, discharge frequency 13 kilohertzs.Then high-voltage power supply power reaches 63 watts, and actual discharge voltage is 11.9 kilovolts, and the temperature-stable of stable reaction post-reactor is at 300 ℃, and the ammonia rates of decomposing and transforming reaches 15%.
The comparative example 8
Repeat comparative example 5, but discharge parameter is set at: 60 volts of the initial voltages of X-former, discharge frequency 13 kilohertzs.Then high-voltage power supply power reaches 72 watts, and actual discharge voltage is 12.8 kilovolts, and the temperature-stable of stable reaction post-reactor is at 370 ℃, and the ammonia rates of decomposing and transforming reaches 19%.
The comparative example 9
Anhydrous liquid ammonia is drawn through reducing valve from storage tank, make the ammonia flow velocity reach 40 ml/min through under meter and mediation valve control, (Fig. 1) sends into the plate plasma discharge reactor from inlet mouth 5.The structure and parameter of reactor drum is identical with embodiment 1, but between high-pressure stage metal sheet and earthing pole metal sheet, has no medium.Ammonia gets into reactor drum by opening for feed 5, and the air in the metathesis reactor exports 9 outflow reactors via splitting gas.After ammonia flow is stablized in the question response device; Give high voltage power supply 10 energisings; Then through voltage regulator, frequency regulator and X-former on the high-voltage power supply; Ac high-voltage progressively is loaded on the metal sheet high-voltage discharging electrode 1 of reactor drum, until the metal high-voltage discharging electrode of reactor drum directly with metal sheet earthing pole 7 between the said ebb-flow discharge of generation.Discharge is difficult to cause, and is extremely unstable, between metal sheet, produces the light beam of vacillating, and is easy to bury in oblivion in region of discharge edge.
Embodiment 13
Anhydrous liquid ammonia is drawn through reducing valve from storage tank, make the ammonia flow velocity reach 40 ml/min through under meter and mediation valve control, (Fig. 2) sends into the plate plasma discharge reactor from opening for feed 5.The metal sheet high-voltage discharging electrode 1 of reactor drum adopts common stainless steel, 50 millimeters of diameters, and 3 millimeters of thickness, the insulated enclosure 2 between itself and the reactor shell adopts polytetrafluoroethylmaterial materials.50 millimeters of the metal sheet diameters of center of area vertical fixing metal wire ground-electrode, 3 millimeters of thickness are fixed on reactor shell inside with polytetrafluoroethylmaterial material.3 millimeters of wire diameter; Stretch out 1 millimeter of metal sheet and taper off to a point; Its most advanced and sophisticated and 4 millimeters of high-pressure metal electrode interpole gaps, the insulation block media plate of 3 millimeters of center of area perforates of parallel placement between two metal electrodes, dielectric is selected quartz material for use; Thick 1 millimeter, all be 2 millimeters with the distance of electrode plate with high voltage and ground connection pole plate.On the reactor wall between earthing pole and the block media plate, offer the ammonia feed mouth, 2 millimeters of diameters; On the reactor wall between high-pressure stage and the block media plate, offer the splitting gas discharge port, 2 millimeters of diameters.The housing 3 usefulness polytetrafluoroethylmaterial materials of this reactor drum are processed, 70 millimeters of external diameters, 60 millimeters of internal diameters, 50 millimeters of region of discharge diameters.The outer heat-insulation and heat-preservation material of housing adopts asbestos.Ammonia gets into reactor drum by opening for feed 5, through the perforate on the block media, exports 9 outflow reactors via splitting gas again.After ammonia flow is stablized in the question response device; Give high voltage power supply 10 energisings; Then through voltage regulator, frequency regulator and X-former on the high-voltage power supply; Ac high-voltage progressively is loaded on the metal sheet high-voltage discharging electrode 1 of reactor drum, until the metal high-voltage discharging electrode of reactor drum 1 through the said ebb-flow discharge of generation between the aperture on the dielectric 4 and earthing pole metal wire 7 tips.Discharge parameter is set at: 70 volts of the initial voltages of X-former, discharge frequency 13 kilohertzs.Then high-voltage power supply power reaches 21 watts, and actual discharge voltage is 3.2 kilovolts, and the temperature-stable of stable reaction post-reactor is at 106 ℃, and the ammonia rates of decomposing and transforming reaches 24%.
Embodiment 14
Repeat embodiment 13, but discharge parameter is set at: 80 volts of the initial voltages of X-former, discharge frequency 13 kilohertzs.Then high-voltage power supply power reaches 24 watts, and actual discharge voltage is 3.5 kilovolts, and the temperature-stable of stable reaction post-reactor is at 138 ℃, and the ammonia rates of decomposing and transforming reaches 27%.
Embodiment 15
Repeat embodiment 13, but discharge parameter is set at: 90 volts of the initial voltages of X-former, discharge frequency 13 kilohertzs.Then high-voltage power supply power reaches 27 watts, and actual discharge voltage is 3.9 kilovolts, and the temperature-stable of stable reaction post-reactor is at 156 ℃, and the ammonia rates of decomposing and transforming reaches 31%.
Embodiment 16
Repeat embodiment 13, but discharge parameter is set at: 100 volts of the initial voltages of X-former, discharge frequency 13 kilohertzs.Then high-voltage power supply power reaches 29 watts, and actual discharge voltage is 3.9 kilovolts, and the temperature-stable of stable reaction post-reactor is at 213 ℃, and the ammonia rates of decomposing and transforming reaches 37%.
Embodiment 17
Repeat embodiment 13, but change the feed ammonia airshed into 100ml/min.Discharge parameter is set at: 70 volts of the initial voltages of X-former, discharge frequency 13 kilohertzs.Then high-voltage power supply power reaches 20 watts, and actual discharge voltage is 3.4 kilovolts, and the temperature-stable of stable reaction post-reactor is at 100 ℃, and the ammonia rates of decomposing and transforming reaches 14%.
Embodiment 18
Repeat embodiment 17, but discharge parameter is set at: 80 volts of the initial voltages of X-former, discharge frequency 13 kilohertzs.Then high-voltage power supply power reaches 24 watts, and actual discharge voltage is 3.7 kilovolts, and the temperature-stable of stable reaction post-reactor is at 121 ℃, and the ammonia rates of decomposing and transforming reaches 16%.
Embodiment 19
Repeat embodiment 17, but discharge parameter is set at: 90 volts of the initial voltages of X-former, discharge frequency 13 kilohertzs.Then high-voltage power supply power reaches 26 watts, and actual discharge voltage is 3.8 kilovolts, and the temperature-stable of stable reaction post-reactor is at 161 ℃, and the ammonia rates of decomposing and transforming reaches 19%.
Embodiment 20
Repeat embodiment 17, but discharge parameter is set at: 100 volts of the initial voltages of X-former, discharge frequency 13 kilohertzs.Then high-voltage power supply power reaches 30 watts, and actual discharge voltage is 3.9 kilovolts, and the temperature-stable of stable reaction post-reactor is at 200 ℃, and the ammonia rates of decomposing and transforming reaches 21%.
Embodiment 21
Repeat embodiment 13, but change the distance between earthing pole wire-tip and the high-pressure stage discharge plate into 6 millimeters by 4 millimeters, the distance of dielectric and electrode plate with high voltage and ground connection pole plate all becomes 3 millimeters.Discharge parameter is set at: 80 volts of the initial voltages of X-former, discharge frequency 13 kilohertzs.Then high-voltage power supply power reaches 26 watts, and actual discharge voltage is 3.8 kilovolts, and the temperature-stable of stable reaction post-reactor is at 134 ℃, and the ammonia rates of decomposing and transforming reaches 35%.
Embodiment 22
Repeat embodiment 21, but discharge parameter is set at: 100 volts of the initial voltages of X-former, discharge frequency 13 kilohertzs.Then high-voltage power supply power reaches 32 watts, and actual discharge voltage is 4.3 kilovolts, and the temperature-stable of stable reaction post-reactor is at 182 ℃, and the ammonia rates of decomposing and transforming reaches 41%.
Embodiment 23
Repeat embodiment 13, but change the distance between earthing pole wire-tip and the high-pressure stage discharge plate into 10 millimeters by 4 millimeters, the distance of dielectric and electrode plate with high voltage and ground connection pole plate all becomes 5 millimeters.Discharge parameter is set at: 100 volts of the initial voltages of X-former, discharge frequency 13 kilohertzs.Then high-voltage power supply power reaches 40 watts, and actual discharge voltage is 4.4 kilovolts, and the temperature-stable of stable reaction post-reactor is at 214 ℃, and the ammonia rates of decomposing and transforming reaches 51%.
Embodiment 24
Repeat embodiment 13, but change the distance between earthing pole wire-tip and the high-pressure stage discharge plate into 15 millimeters by 4 millimeters, the distance of dielectric and electrode plate with high voltage and ground connection pole plate all becomes 7.5 millimeters.Discharge parameter is set at: 120 volts of the initial voltages of X-former, discharge frequency 13 kilohertzs.Then high-voltage power supply power reaches 41 watts, and actual discharge voltage is 4.9 kilovolts, and the temperature-stable of stable reaction post-reactor is at 236 ℃, and the ammonia rates of decomposing and transforming reaches 62%.
The comparative example 10
Anhydrous liquid ammonia is drawn through reducing valve from storage tank, make the ammonia flow velocity reach 40 ml/min through under meter and mediation valve control, (Fig. 2) sends into the plate plasma discharge reactor from opening for feed 5.The structure of this reactor drum is identical with embodiment 13 with characteristic parameter, but changes the perforate medium into complete medium, and is placed on the high-pressure polar plate surface.Ammonia gets into reactor drum by opening for feed 5, through the perforate on the block media, exports 9 outflow reactors via splitting gas again.After ammonia flow is stablized in the question response device; Give high voltage power supply 10 energisings; Then through voltage regulator, frequency regulator and X-former on the high-voltage power supply; Ac high-voltage progressively is loaded on the metal sheet high-voltage discharging electrode 1 of reactor drum, until the metal high-voltage discharging electrode of reactor drum 1 logical with earthing pole metal wire 7 tips between generation cone shape dielectric impedance plasma discharge passage.Discharge parameter is set at: 30 volts of the initial voltages of X-former, discharge frequency 13 kilohertzs.Then high-voltage power supply power reaches 27 watts, and actual discharge voltage is 9.8 kilovolts, and the temperature-stable of stable reaction post-reactor is at 114 ℃, and the ammonia rates of decomposing and transforming reaches 4%.
The comparative example 11
Repeat comparative example 10, but discharge parameter is set at: 35 volts of the initial voltages of X-former, discharge frequency 13 kilohertzs.Then high-voltage power supply power reaches 35 watts, and actual discharge voltage is 10.4 kilovolts, and the temperature-stable of stable reaction post-reactor is at 245 ℃, and the ammonia rates of decomposing and transforming reaches 10%.
The comparative example 12
Repeat comparative example 10, but discharge parameter is set at: 40 volts of the initial voltages of X-former, discharge frequency 13 kilohertzs.Then high-voltage power supply power reaches 42 watts, and actual discharge voltage is 11.0 kilovolts, and the temperature-stable of stable reaction post-reactor is at 321 ℃, and the ammonia rates of decomposing and transforming reaches 15%.
The comparative example 13
Repeat comparative example 10, but discharge parameter is set at: 45 volts of the initial voltages of X-former, discharge frequency 13 kilohertzs.Then high-voltage power supply power reaches 48 watts, and actual discharge voltage is 11.6 kilovolts, and the temperature-stable of stable reaction post-reactor is at 379 ℃, and the ammonia rates of decomposing and transforming reaches 19%.
The comparative example 14
Anhydrous liquid ammonia is drawn through reducing valve from storage tank, make the ammonia flow velocity reach 40 ml/min through under meter and mediation valve control, (Fig. 2) sends into the plate plasma discharge reactor from opening for feed 5.The structure of this reactor drum is identical with embodiment 13 with characteristic parameter, but between high-pressure stage metal sheet and earthing pole metal sheet, has no medium.Ammonia gets into reactor drum by opening for feed 5, and the air in the metathesis reactor exports 9 outflow reactors via splitting gas.After ammonia flow is stablized in the question response device; Give high voltage power supply 10 energisings; Through voltage regulator, frequency regulator and X-former on the high-voltage power supply, ac high-voltage progressively is loaded on the metal sheet high-voltage discharging electrode 1 of reactor drum then, until the metal high-voltage discharging electrode 1 of reactor drum directly with earthing pole metal wire 7 tips between the unsettled corona discharge of generation; Can produce intense radiation to consumer on every side, disturb its normal operation.Discharge parameter is set at: 70 volts of the initial voltages of X-former, discharge frequency 13 kilohertzs.Then high-voltage power supply power reaches 21 watts, and actual discharge voltage is 3.2 kilovolts, and the temperature-stable of stable reaction post-reactor is at 100 ℃, and the ammonia rates of decomposing and transforming reaches 18%.
The comparative example 15
Repeat comparative example 14, but discharge parameter is set at: 80 volts of the initial voltages of X-former, discharge frequency 13 kilohertzs.Then high-voltage power supply power reaches 24 watts, and actual discharge voltage is 3.5 kilovolts, and the temperature-stable of stable reaction post-reactor is at 134 ℃, and the ammonia rates of decomposing and transforming reaches 23%.
The comparative example 16
Repeat comparative example 14, but discharge parameter is set at: 90 volts of the initial voltages of X-former, discharge frequency 13 kilohertzs.Then high-voltage power supply power reaches 27 watts, and actual discharge voltage is 3.7 kilovolts, and the temperature-stable of stable reaction post-reactor is at 150 ℃, and the ammonia rates of decomposing and transforming reaches 25%.
The comparative example 17
Repeat comparative example 14, but discharge parameter is set at: 100 volts of the initial voltages of X-former, discharge frequency 13 kilohertzs.Then high-voltage power supply power reaches 28 watts, and actual discharge voltage is 3.8 kilovolts, and the temperature-stable of stable reaction post-reactor is at 208 ℃, and the ammonia rates of decomposing and transforming reaches 33%.
Embodiment 25
Anhydrous liquid ammonia is drawn through reducing valve from storage tank, make the ammonia flow velocity reach 40 ml/min through under meter and mediation valve control, (Fig. 3) sends into the plate plasma discharge reactor from opening for feed 5.The metal sheet high-voltage discharging electrode 1 of reactor drum adopts common stainless steel, 50 millimeters of diameters, and 3 millimeters of thickness, the insulated enclosure 2 between itself and the reactor shell adopts polytetrafluoroethylmaterial materials.50 millimeters of the metal sheet diameters of center of area vertical fixing grounded metal pipe electrode, 3 millimeters of thickness are fixed on reactor shell inside with polytetrafluoroethylmaterial material, and metal tube is processed by stainless material, 3 millimeters of O.D.T., 2 millimeters of internal diameters.Metal tube stretches out 1 millimeter of metal sheet; 4 millimeters of the mouth of pipe and high-pressure metal electrode interpole gaps, the insulation block media plate of 3 millimeters of center of area perforates of parallel placement between two metal electrodes, dielectric is selected quartz material for use; Thick 1 millimeter, all be 2 millimeters with the distance of electrode plate with high voltage and ground connection pole plate.With the earthing pole metal tube is the ammonia feed mouth; On the reactor wall between high-pressure stage and the block media plate, offer the splitting gas discharge port, 2 millimeters of diameters.The housing 3 usefulness polytetrafluoroethylmaterial materials of this reactor drum are processed, 70 millimeters of external diameters, 60 millimeters of internal diameters, 50 millimeters of region of discharge diameters.The outer heat-insulation and heat-preservation material of housing adopts asbestos.Ammonia gets into reactor drum by opening for feed 5, through the perforate on the block media, exports 9 outflow reactors via splitting gas again.After ammonia flow is stablized in the question response device; Give high voltage power supply 10 energisings; Then through voltage regulator, frequency regulator and X-former on the high-voltage power supply; Ac high-voltage progressively is loaded on the metal sheet high-voltage discharging electrode 1 of reactor drum, until the metal high-voltage discharging electrode of reactor drum 1 through the said ebb-flow discharge of generation between the aperture on the dielectric 4 and earthing pole metal tube 7 mouths of pipe.Discharge parameter is set at: 70 volts of the initial voltages of X-former, discharge frequency 13 kilohertzs.Then high-voltage power supply power reaches 22 watts, and actual discharge voltage is 2.9 kilovolts, and the temperature-stable of stable reaction post-reactor is at 120 ℃, and the ammonia rates of decomposing and transforming reaches 54%.
Embodiment 26
Repeat embodiment 25, but discharge parameter is set at: 80 volts of the initial voltages of X-former, discharge frequency 13 kilohertzs.Then high-voltage power supply power reaches 26 watts, and actual discharge voltage is 3.2 kilovolts, and the temperature-stable of stable reaction post-reactor is at 144 ℃, and the ammonia rates of decomposing and transforming reaches 59%.
Embodiment 27
Repeat embodiment 25, but discharge parameter is set at: 90 volts of the initial voltages of X-former, discharge frequency 13 kilohertzs.Then high-voltage power supply power reaches 33 watts, and actual discharge voltage is 3.5 kilovolts, and the temperature-stable of stable reaction post-reactor is at 164 ℃, and the ammonia rates of decomposing and transforming reaches 71%.
Embodiment 28
Repeat embodiment 25, but discharge parameter is set at: 130 volts of the initial voltages of X-former, discharge frequency 13 kilohertzs.Then high-voltage power supply power reaches 45 watts, and actual discharge voltage is 3.9 kilovolts, and the temperature-stable of stable reaction post-reactor is at 262 ℃, and the ammonia rates of decomposing and transforming reaches 79%.
Embodiment 29
Repeat embodiment 25, but change the earthing pole metal tube into external diameter 6 millimeters, 4 millimeters of internal diameters.Discharge parameter is set at: 70 volts of the initial voltages of X-former, discharge frequency 13 kilohertzs.Then high-voltage power supply power reaches 20 watts, and actual discharge voltage is 2.9 kilovolts, and the temperature-stable of stable reaction post-reactor is at 100 ℃, and the ammonia rates of decomposing and transforming reaches 38%.
Embodiment 30
Repeat embodiment 29, but discharge parameter is set at: 80 volts of the initial voltages of X-former, discharge frequency 13 kilohertzs.Then high-voltage power supply power reaches 23 watts, and actual discharge voltage is 3.2 kilovolts, and the temperature-stable of stable reaction post-reactor is at 125 ℃, and the ammonia rates of decomposing and transforming reaches 46%.
Embodiment 31
Repeat embodiment 29, but discharge parameter is set at: 90 volts of the initial voltages of X-former, discharge frequency 13 kilohertzs.Then high-voltage power supply power reaches 30 watts, and actual discharge voltage is 3.5 kilovolts, and the temperature-stable of stable reaction post-reactor is at 160 ℃, and the ammonia rates of decomposing and transforming reaches 54%.
Embodiment 32
Repeat embodiment 29, but discharge parameter is set at: 130 volts of the initial voltages of X-former, discharge frequency 13 kilohertzs.Then high-voltage power supply power reaches 43 watts, and actual discharge voltage is 3.9 kilovolts, and the temperature-stable of stable reaction post-reactor is at 248 ℃, and the ammonia rates of decomposing and transforming reaches 70%.
Embodiment 33
Repeat embodiment 25, but change the feed ammonia airshed into 100ml/min.Discharge parameter is set at: 70 volts of the initial voltages of X-former, discharge frequency 13 kilohertzs.Then high-voltage power supply power reaches 21 watts, and actual discharge voltage is 2.9 kilovolts, and the temperature-stable of stable reaction post-reactor is at 110 ℃, and the ammonia rates of decomposing and transforming reaches 23%.
Embodiment 34
Repeat embodiment 33, but discharge parameter is set at: 80 volts of the initial voltages of X-former, discharge frequency 13 kilohertzs.Then high-voltage power supply power reaches 24 watts, and actual discharge voltage is 3.3 kilovolts, and the temperature-stable of stable reaction post-reactor is at 124 ℃, and the ammonia rates of decomposing and transforming reaches 26%.
Embodiment 35
Repeat embodiment 33, but discharge parameter is set at: 90 volts of the initial voltages of X-former, discharge frequency 13 kilohertzs.Then high-voltage power supply power reaches 28 watts, and actual discharge voltage is 3.6 kilovolts, and the temperature-stable of stable reaction post-reactor is at 160 ℃, and the ammonia rates of decomposing and transforming reaches 31%.
Embodiment 36
Repeat embodiment 33, but discharge parameter is set at: 130 volts of the initial voltages of X-former, discharge frequency 13 kilohertzs.Then high-voltage power supply power reaches 42 watts, and actual discharge voltage is 3.9 kilovolts, and the temperature-stable of stable reaction post-reactor is at 246 ℃, and the ammonia rates of decomposing and transforming reaches 38%.
Embodiment 37
Repeat embodiment 25, but change the distance between the earthing pole metal tube mouth of pipe and the high-pressure stage discharge plate into 6 millimeters by 4 millimeters, the distance of dielectric and electrode plate with high voltage and ground connection pole plate all becomes 3 millimeters.Discharge parameter is set at: 70 volts of the initial voltages of X-former, discharge frequency 13 kilohertzs.Then high-voltage power supply power reaches 24 watts, and actual discharge voltage is 3.0 kilovolts, and the temperature-stable of stable reaction post-reactor is at 125 ℃, and the ammonia rates of decomposing and transforming reaches 57%.
Embodiment 38
Repeat embodiment 37, but discharge parameter is set at: 90 volts of the initial voltages of X-former, discharge frequency 13 kilohertzs.Then high-voltage power supply power reaches 34 watts, and actual discharge voltage is 3.8 kilovolts, and the temperature-stable of stable reaction post-reactor is at 168 ℃, and the ammonia rates of decomposing and transforming reaches 73%.
Embodiment 39
Repeat embodiment 25, but change the distance between the earthing pole metal tube mouth of pipe and the high-pressure stage discharge plate into 10 millimeters by 4 millimeters, the distance of dielectric and electrode plate with high voltage and ground connection pole plate all becomes 5 millimeters.Discharge parameter is set at: 100 volts of the initial voltages of X-former, discharge frequency 13 kilohertzs.Then high-voltage power supply power reaches 42 watts, and actual discharge voltage is 4.9 kilovolts, and the temperature-stable of stable reaction post-reactor is at 188 ℃, and the ammonia rates of decomposing and transforming reaches 72%.
Embodiment 40
Repeat embodiment 25, but change the distance between the earthing pole metal tube mouth of pipe and the high-pressure stage discharge plate into 15 millimeters by 4 millimeters, the distance of dielectric and electrode plate with high voltage and ground connection pole plate all becomes 7.5 millimeters.Discharge parameter is set at: 120 volts of the initial voltages of X-former, discharge frequency 13 kilohertzs.Then high-voltage power supply power reaches 48 watts, and actual discharge voltage is 5.6 kilovolts, and the temperature-stable of stable reaction post-reactor is at 284 ℃, and the ammonia rates of decomposing and transforming reaches 79%.
The comparative example 18
Anhydrous liquid ammonia is drawn through reducing valve from storage tank, make the ammonia flow velocity reach 40 ml/min through under meter and mediation valve control, (Fig. 3) sends into the plate plasma discharge reactor from opening for feed 5.The structure of this reactor drum is identical with embodiment 25 with characteristic parameter, but changes the perforate medium into complete medium, and is placed on the high-pressure stage metal sheet surface.Ammonia gets into reactor drum by opening for feed 5, and the air in the metathesis reactor exports 9 outflow reactors via splitting gas.After ammonia flow is stablized in the question response device; Give high voltage power supply 10 energisings; Then through voltage regulator, frequency regulator and X-former on the high-voltage power supply; Ac high-voltage progressively is loaded on the metal sheet high-voltage discharging electrode 1 of reactor drum, between the dielectric 4 that covers on metal tube earthing pole 7 mouths of pipe of reactor drum and the high-pressure metal plate discharge electrode 1, produces Rotary-table shape dielectric impedance plasma discharge passage.Discharge parameter is set at: 25 volts of the initial voltages of X-former, discharge frequency 13 kilohertzs.Then high-voltage power supply power reaches 27 watts, and actual discharge voltage is 9.9 kilovolts, and the temperature-stable of stable reaction post-reactor is at 114 ℃, and the ammonia rates of decomposing and transforming reaches 9%.
The comparative example 19
Repeat comparative example 18, but discharge parameter is set at: 30 volts of the initial voltages of X-former, discharge frequency 13 kilohertzs.Then high-voltage power supply power reaches 36 watts, and actual discharge voltage is 10.8 kilovolts, and the temperature-stable of stable reaction post-reactor is at 245 ℃, and the ammonia rates of decomposing and transforming reaches 14%.
The comparative example 20
Repeat comparative example 18, but discharge parameter is set at: 35 volts of the initial voltages of X-former, discharge frequency 13 kilohertzs.Then high-voltage power supply power reaches 43 watts, and actual discharge voltage is 11.1 kilovolts, and the temperature-stable of stable reaction post-reactor is at 321 ℃, and the ammonia rates of decomposing and transforming reaches 21%.
The comparative example 21
Repeat comparative example 18, but discharge parameter is set at: 40 volts of the initial voltages of X-former, discharge frequency 13 kilohertzs.Then high-voltage power supply power reaches 50 watts, and actual discharge voltage is 11.9 kilovolts, and the temperature-stable of stable reaction post-reactor is at 359 ℃, and the ammonia rates of decomposing and transforming reaches 27%.
The comparative example 22
Anhydrous liquid ammonia is drawn through reducing valve from storage tank, make the ammonia flow velocity reach 40 ml/min through under meter and mediation valve control, (Fig. 3) sends into the plate plasma discharge reactor from opening for feed 5.The structure of this reactor drum is identical with embodiment 25 with characteristic parameter, but between the high-pressure stage metal sheet and the earthing pole metal tube mouth of pipe, has no block media.Ammonia gets into reactor drum by opening for feed 5, and the air in the metathesis reactor exports 9 outflow reactors via splitting gas.After ammonia flow is stablized in the question response device; Give high voltage power supply 10 energisings; Through voltage regulator, frequency regulator and X-former on the high-voltage power supply, ac high-voltage progressively is loaded on the metal sheet high-voltage discharging electrode 1 of reactor drum then, directly produces unsettled corona discharge until metal tube earthing pole 7 mouths of pipe and the high-pressure metal plate discharge electrode 1 of reactor drum; Can produce intense radiation to consumer on every side, disturb its normal operation.Discharge parameter is set at: 70 volts of the initial voltages of X-former, discharge frequency 13 kilohertzs.Then high-voltage power supply power reaches 21 watts, and actual discharge voltage is 2.8 kilovolts, and the temperature-stable of stable reaction post-reactor is at 117 ℃, and the ammonia rates of decomposing and transforming reaches 50%.
The comparative example 23
Repeat comparative example 22, but discharge parameter is set at: 80 volts of the initial voltages of X-former, discharge frequency 13 kilohertzs.Then high-voltage power supply power reaches 24 watts, and actual discharge voltage is 3.2 kilovolts, and the temperature-stable of stable reaction post-reactor is at 141 ℃, and the ammonia rates of decomposing and transforming reaches 54%.
The comparative example 24
Repeat comparative example 22, but discharge parameter is set at: 90 volts of the initial voltages of X-former, discharge frequency 13 kilohertzs.Then high-voltage power supply power reaches 32 watts, and actual discharge voltage is 3.5 kilovolts, and the temperature-stable of stable reaction post-reactor is at 153 ℃, and the ammonia rates of decomposing and transforming reaches 66%.
The comparative example 25
Repeat comparative example 22, but discharge parameter is set at: 130 volts of the initial voltages of X-former, discharge frequency 13 kilohertzs.Then high-voltage power supply power reaches 44 watts, and actual discharge voltage is 3.9 kilovolts, and the temperature-stable of stable reaction post-reactor is at 247 ℃, and the ammonia rates of decomposing and transforming reaches 71%.
The comparative example 26
Anhydrous liquid ammonia is drawn through reducing valve from storage tank; And control through under meter and mediation valve and to make flow velocity reach 40 ml/min; Send into the dielectric barrier discharge plasma reactor drum from the ammonia inlet; The patent CN200610200563.0 in early stage that the scantlings of the structure of this reactor drum and material are seen us does not adorn any catalyzer in the reactor drum.With the air in the charging ammonia metathesis reactor, discharged from the splitting gas outlet by metathetical gas.Switch on to high voltage power supply; Then through voltage regulator, frequency regulator and X-former on the high-voltage power supply; Ac high-voltage progressively is loaded on the metal high-voltage discharging electrode of reactor drum, between the metal high-voltage discharging electrode of reactor drum and metal earthing pole, in the presence of block media, produces said dielectric barrier discharge (being thread discharge).Discharge parameter is set at: 38 volts of the initial voltages of X-former, discharge frequency 12 kilohertzs.Then high-voltage power supply power reaches 11 watts, and actual discharge voltage is 9.4 kilovolts, and the temperature-stable of stable reaction post-reactor is at 381 ℃, and the ammonia rates of decomposing and transforming reaches 2%.
The comparative example 27
Repeat comparative example 26, but discharge parameter is set at: 41 volts of the initial voltages of X-former, discharge frequency 12 kilohertzs.Then high-voltage power supply power reaches 25 watts, and actual discharge voltage is 10.3 kilovolts, and the temperature-stable of stable reaction post-reactor is at 409 ℃, and the ammonia rates of decomposing and transforming reaches 9%.
The comparative example 28
Repeat comparative example 26, but discharge parameter is set at: 44 volts of the initial voltages of X-former, discharge frequency 12 kilohertzs.Then high-voltage power supply power reaches 30 watts, and actual discharge voltage is 11.1 kilovolts, and the temperature-stable of stable reaction post-reactor is at 466 ℃, and the ammonia rates of decomposing and transforming reaches 10%.
The comparative example 29
Repeat comparative example 26, but discharge parameter is set at: 48 volts of the initial voltages of X-former, discharge frequency 12 kilohertzs.Then high-voltage power supply power reaches 41 watts, and actual discharge voltage is 11.9 kilovolts, and the temperature-stable of stable reaction post-reactor is at 472 ℃, and the ammonia rates of decomposing and transforming reaches 15%.
The comparative example 30
Repeat comparative example 26, but discharge parameter is set at: 51 volts of the initial voltages of X-former, discharge frequency 12 kilohertzs.Then high-voltage power supply power reaches 48 watts, and actual discharge voltage is 12.8 kilovolts, and the temperature-stable of stable reaction post-reactor is at 504 ℃, and the ammonia rates of decomposing and transforming reaches 18%.

Claims (4)

1. plate type plasma reactor that is used for preparing hydrogen by ammonia decomposition, ammonia decomposition reaction carries out in the plate plasma discharge reactor with perforate block media plate; It is characterized in that,
The block media plate of at least one perforate is set between the high voltage terminal of plate type plasma reactor and ground-electrode, and the distance of itself and two electrodes is regulated arbitrarily; The dielectric impedance plate is divided into two portions with reactor drum, offers the ammonia feed mouth in earthing pole one side, offers the splitting gas discharge port in high-pressure stage one side; Perforate on the block media plate is a discharge channel, is again the reactant necessary channel;
The high voltage terminal of plate-type reactor and ground-electrode are taked any in following three kinds of modes:
(1) high voltage terminal of plate-type reactor and ground-electrode are respectively two metal sheets, and two metal electrode boards are fixed in the housing of reactor drum abreast, and the vertical range between two plates is an interpole gap; On the reactor wall of earthing pole one side, offer the ammonia feed mouth, on the reactor wall of high-pressure stage one side, offer the splitting gas discharge port; The metal sheet center of area of the position of opening of block media plate and ground-electrode is relative;
(2) high voltage terminal of plate-type reactor is a metal sheet, and ground-electrode is a metal wire; To be fixed on abreast in the housing of reactor drum as the metal sheet of vertical fixing ground-electrode metal wire on the metal sheet of high voltage terminal and the center of area, the grounded metal endpoints is an interpole gap to the distance of electrode plate with high voltage; On the reactor wall of earthing pole one side, offer the ammonia feed mouth, on the reactor wall of high-pressure stage one side, offer the splitting gas discharge port; The position of opening of block media plate is relative with the ground-electrode metal wire;
(3) high voltage terminal of plate-type reactor is a metal sheet, and ground-electrode is a metal tube; To be fixed on abreast in the housing of reactor drum as the metal sheet of vertical fixing ground-electrode metal tube on the metal sheet of high voltage terminal and the center of area, the grounded metal pipe mouth of pipe is an interpole gap to the distance of electrode plate with high voltage; The double ammonia feed mouth of doing of earthing pole metal tube; On the reactor wall of high-pressure stage one side, offer the splitting gas discharge port; The position of opening of block media plate is relative with the ground-electrode metal tube;
Two interpole gaps of above-mentioned reactor drum are got the 0.5-15 millimeter; The external diameter scope of the diameter of earthing pole metal wire or metal tube is the 0.5-20 millimeter; The bore size 0.5-30 millimeter of block media plate; Ammonia feed mouth size range is the 0.5-10 millimeter; Splitting gas discharge port size range is the 0.5-12 millimeter.
2. a kind of plate type plasma reactor that is used for preparing hydrogen by ammonia decomposition according to claim 1, its characteristic are that also two interpole gaps of above-mentioned reactor drum are got the 4-8 millimeter; The external diameter scope of the diameter of earthing pole metal wire or metal tube is the 2-6 millimeter; The bore size of block media plate is selected the 2-8 millimeter; Ammonia feed mouth size range is the 2-6 millimeter; Splitting gas discharge port size range is the 2-8 millimeter.
3. a kind of plate type plasma reactor that is used for preparing hydrogen by ammonia decomposition according to claim 1, its characteristic also be, the housing of above-mentioned plate type plasma reactor is processed with insulating material or the metal and the nonmetallic composite that meet the high voltage electric insulating Design; Plate type plasma reactor uses the place of metallic substance, with any surface finish, physical strength is high, high temperature resistant and do not process with the plasma body of ammonia and the metallic substance of ammonia degradation production generation chemical reaction; The block media plate with any surface finish, heat-resisting, physical strength is high and do not process with the plasma body of ammonia and the insulating material of ammonia degradation production generation chemical reaction; The external covering insulation material of reactor enclosure.
4. a kind of plate type plasma reactor that is used for preparing hydrogen by ammonia decomposition according to claim 3, its characteristic are that also the plate type plasma reactor housing is with quartz, hard glass, alumina-ceramic, tetrafluoroethylene; Use the place of metallic substance, use stainless material; The block media plate is with glass, quartz, hard glass, epoxy resin, mica or alumina-ceramic.
CN2010101658956A 2010-05-07 2010-05-07 Plate type plasma reactor for hydrogen production through ammonia decomposition Expired - Fee Related CN101863455B (en)

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